US20220181627A1 - Cathode additive for lithium secondary battery, preparation method therefor, cathode for lithium secondary battery, comprising same, and lithium secondary battery comprising same - Google Patents

Cathode additive for lithium secondary battery, preparation method therefor, cathode for lithium secondary battery, comprising same, and lithium secondary battery comprising same Download PDF

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US20220181627A1
US20220181627A1 US17/298,778 US201917298778A US2022181627A1 US 20220181627 A1 US20220181627 A1 US 20220181627A1 US 201917298778 A US201917298778 A US 201917298778A US 2022181627 A1 US2022181627 A1 US 2022181627A1
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positive electrode
chemical formula
secondary battery
lithium secondary
additive
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Jong Il Park
Jae Myung LEE
Geun HWANGBO
Sang Cheol Nam
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Research Institute of Industrial Science and Technology RIST
Posco Holdings Inc
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Research Institute of Industrial Science and Technology RIST
Posco Holdings Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode additive for a lithium secondary battery, a manufacturing method thereof, a positive electrode for a lithium secondary battery including the same, and a lithium secondary battery including the same. More specifically, it relates to a positive electrode additive for a lithium secondary battery that is a non-reversible capacity improving additive for improving the non-reversible characteristic of a negative electrode, a manufacturing method thereof, a positive electrode for a lithium secondary battery including the same, and a lithium secondary battery including the same.
  • the lithium secondary battery is manufactured in the form of a small battery with high performance and is used as an energy storage source for mobile information communication devices including smartphones, laptops, and computers. Recently, a research is being conducted to manufacture a high-output, large-sized battery and use it in an electric vehicle, a hybrid electric vehicle, and the like.
  • lithium-containing cobalt oxide (LiCoO 2 ) is mainly used, and in addition, lithium-containing manganese oxide such as LiMn 2 O 4 having a spinel crystal structure, and lithium-containing nickel oxide (LiNiO 2 ) are also used.
  • Carbon material is mainly used as a negative active material, and lithium metal and sulfur compound are also considered.
  • the theoretical specific capacity of pure silicon (Si) is 4200 mAh/g, which is 372 of graphite carbon. Since a capacity of silicon is superbly larger than that of graphite, lithium secondary batteries using the Si-based active material are attracting a lot of attention, and some are used as electrodes mixed with carbon materials.
  • the negative electrode has low non-reversible efficiency compared to the positive electrode, the amount of negative active material is excessively input and that makes negatively effects of the energy density of the battery.
  • a lithium composite oxide containing nickel (Ni) of high-capacity, cobalt (Co), and manganese (Mn) is generally used as a positive active material, and a silicon-carbon composite negative active material may be used.
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • the non-reversible efficiency of the positive electrode during initial charging and discharging including the initial charging is very high as 90% or more, but the initial non-reversible efficiency of the negative electrode is at the level of 80 to 90%.
  • a small amount of negative active material is input for the design of the battery together with the positive electrode of lithium composite oxide containing the high nickel-containing nickel (Ni), cobalt (Co) and manganese (Mn).
  • the amount of carbon-based negative active material is reduced. It may be difficult to design efficiently.
  • the present invention relates to a positive electrode additive for a lithium secondary battery, a manufacturing method thereof, a positive electrode for a lithium secondary battery including the same, and a lithium secondary battery including the same. More specifically, it relates to a positive electrode additive for a lithium secondary battery that is a non-reversible capacity improving additive for improving the non-reversible characteristic of a negative electrode, a manufacturing method thereof, a positive electrode for a lithium secondary battery including the same, and a lithium secondary battery including the same.
  • a positive electrode additive for a lithium secondary battery according to an exemplary embodiment of the present invention is represented by Chemical Formula 1 below.
  • the positive electrode additive may be coated with one or more of boron (B) and tungsten (W).
  • Another positive electrode additive for a lithium secondary battery includes a core represented by Chemical Formula 2 below; and a coating layer comprising at least one of boron (B) and tungsten (W).
  • the manufacturing method of the positive electrode additive for lithium secondary battery according to an exemplary embodiment of the present invention includes:
  • the doping raw material comprises at least one of boron (B) and tungsten (W).
  • the lithium raw material is at least one selected from the group consisting of Li 2 CO 3 , LiOH, C 2 H 3 LiO 2 , LiNO 3 , Li 2 SO 4 , Li 2 SO 3 , Li 2 O, Li 2 O 2 , and LiCl.
  • a mixing ratio of the precursor particle and the lithium raw material may be 1:5.9 to 1:6.1 by molar ratio.
  • a mixing ratio of the doping raw material to the mixture may be 0.001 to 0.02 by molar ratio.
  • the calcination condition is in an inert atmosphere for 1 to 15 hours at a temperature range of 600 to 800° C.
  • the doping raw material comprises at least one of boron (B) and tungsten (W).
  • a mixing ratio of the doping raw material to the compound represented by the Chemical Formula 3 may be 0.001 to 0.02 by molar ratio.
  • a calcining condition may be in an inert atmosphere for 1 to 10 hours in a temperature range of 250 to 450° C.
  • the method further comprises forming a coating layer by mixing the coating raw material with the lithium metal oxide and calcining that; and the coating raw material comprises at least one of boron (B) and tungsten (W).
  • the positive electrode for a lithium secondary battery includes:
  • the positive electrode active material layer comprises a positive electrode active material and a positive electrode additive
  • the positive electrode additive is represented by the following Chemical Formula 3, and
  • the positive electrode additive is 0.1 to 7 wt %.
  • the positive electrode additive is decomposed during initial charging and discharging and converted into a Li supply source and a compound represented by Chemical Formula 4 below.
  • the positive electrode additive is coated with at least one of boron (B) and tungsten (W).
  • the lithium secondary battery according to an exemplary embodiment of the present invention includes:
  • the positive electrode comprises the above-mentioned positive electrode additive.
  • a positive electrode additive for a secondary battery which is a non-reversible capacity improvement additive for improving the non-reversible characteristic of the negative electrode according to the present invention, can be used. This makes it possible to exhibit 100% efficiency of the battery. In addition, it is possible to increase the cycle-life of the battery by solving the problem of gelation or gas generation due to the non-reversible capacity improvement additive.
  • FIG. 1 shows the initial charge capacity (0.1C charge) of the positive electrode additive for a lithium secondary battery according to an exemplary embodiment of the present invention.
  • FIG. 2 shows the initial charge capacity (0.1C charge) of the positive electrode additive for a lithium secondary battery according to an exemplary embodiment of the present invention.
  • FIG. 3 shows the XRD analysis result of the positive electrode additive for lithium secondary battery according to an exemplary embodiment of the present invention.
  • first, second and third are used to describe various parts, components, regions, layers and/or sections, but are not limited thereto. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, the first part, component, region, layer or section described below may be referred to as the second part, component, region, layer or section without departing from the scope of the present invention.
  • the term “combination thereof” included in the expression of the Markush format means at least one mixture or combination selected from the group consisting of constituent elements described in the expression of the Markush format. It means to include one or more selected from the group consisting of the above components.
  • a part when it is mentioned that a part is “on” or “above” the other part, it may be directly on or above the other part, or another part may be accompanied in between. In contrast, when a part refers to being “directly on” another part, there is no intervening part in between.
  • % means wt %, and 1 ppm is 0.0001 wt %.
  • a positive electrode additive for a lithium secondary battery according to an exemplary embodiment of the present invention is represented by Chemical Formula 1 below.
  • the additive represented by Chemical Formula 1 below is doped lithium rich cobalt oxide.
  • the positive electrode additive may be coating at least one of boron (B) and tungsten (W).
  • B boron
  • W tungsten
  • the positive electrode additive may be coating at least one of boron (B) and tungsten (W).
  • B boron
  • W tungsten
  • the cathode material slurry which is a problem when manufacturing electrode slurry, so there is no problem even if a lot of this additive is used during slurry manufacturing.
  • Li 2 O and Li 2 CO 3 remaining on the additive surface are changed into stable lithium boron compound (LiB 4 O 7 ) and lithium tungsten compound (Li 2 WO 4 ) by reacting boron compound and tungsten compound. Therefore, it is possible to reduce the PVDF binder gelation by basic lithium during slurry production. It can be used more stably in the process of manufacturing the electrode.
  • lithium in the form of lithium carbonate (Li 2 CO 3 ) and lithium hydroxide (LiOH), which do not mainly participate in the reaction, is unavoidably present on the surface of lithium composite oxide containing Ni and Co, and this is called residual lithium.
  • LiOH in residual lithium can react with CO 2 in air or CO 2 generated by decomposition of carbonate-based electrolyte solution to form Li 2 CO 3 .
  • Li 2 CO 3 may react with HF again to generate CO 2 gas.
  • Such gas generation causes problems such as a decrease in the initial capacity of the battery and a decrease in initial charging and discharge efficiency.
  • boron or tungsten is added as described above, the amount of residual lithium can be reduced and the initial charge capacity can be improved.
  • Another positive electrode additive for a lithium secondary battery includes a core represented by Chemical Formula 2 below; and a coating layer comprising at least one of boron (B) and tungsten (W).
  • 0.9 ⁇ x ⁇ 1.1 That is, a coating layer containing at least one of boron (B) and tungsten (W) is coated on overlithiated lithium cobalt oxide.
  • B boron
  • W tungsten
  • the positive electrode additives mentioned above were developed by the inventors of the present invention after repeated in-depth research and various experiments. It can be effectively used for non-reversible efficiency design, and the conductive network configuration of the electrode can be improved due to its high conductivity.
  • the present invention has been achieved by developing an additive that reduces gelation caused by excessive residual lithium.
  • the positive electrode additives according to an exemplary embodiment of the present invention are used together with the positive electrode active material to achieve 100% efficiency of the battery. Due to the non-reversible capacity improvement effect of the positive electrode additive, the cycle-life of the battery can be increased by solving the problem of gelation and gas generation.
  • the positive electrode additive may exhibit high conductivity in some cases. Therefore, the conductive network configuration of the electrode can also be improved.
  • the manufacturing method of the positive electrode additive for lithium secondary battery according to an exemplary embodiment of the present invention includes:
  • the doping raw material comprises at least one of boron (B) and tungsten (W).
  • the lithium raw material is at least one selected from the group consisting of Li 2 CO 3 , LiOH, C 2 H 3 LiO 2 , LiNO 3 , Li 2 SO 4 , Li 2 SO 3 , Li 2 O, Li 2 O 2 , and LiCl.
  • the compound is a boron compound, and may be expressed as H 3 BO 3 , B 2 O 3 , or the like.
  • the compound is a tungsten compound, and can be expressed as WO 3 , H 2 WO 4 , (NH 4 ) 10 (H 2 W 12 O 42 ).4H 2 O, (NH 4 ) 6 H 2 W 12 O 4 0.XH 2 O, etc.
  • a mixing ratio of the precursor particle and the lithium raw material may be 1:5.9 to 1:6.1 by molar ratio.
  • a mixing ratio of the doping raw material to the mixture may be 0.001 to 0.02 by molar ratio.
  • the calcination condition is in an inert atmosphere for 1 to 15 hours at a temperature range of 600 to 800° C. More specifically, it may be calcined for 1 to 10 hours.
  • the additive can be obtained by pulverizing and classifying the calcined product prepared by calcining the mixture.
  • the doping raw material comprises at least one of boron (B) and tungsten (W). That is, it is a method of manufacturing a doped positive electrode additive by mixing an already prepared undoped positive electrode additive with a doping raw material, which is different from the above manufacturing method.
  • a mixing ratio of the doping raw material to the compound represented by the Chemical Formula 3 may be 0.001 to 0.02 by molar ratio.
  • a calcining condition may be in an inert atmosphere for 1 to 10 hours in a temperature range of 250 to 450° C.
  • the method further comprises forming a coating layer by mixing the coating raw material with the lithium metal oxide and calcining that; and the coating raw material comprises at least one of boron (B) and tungsten (W). That is, the method may further include forming a coating layer.
  • the positive electrode additive manufactured according to an exemplary embodiment of the present invention may be usefully used in the positive electrode of a lithium secondary battery.
  • the positive electrode for a lithium secondary battery includes:
  • the positive electrode active material layer comprises a positive electrode active material and a positive electrode additive
  • the positive electrode additive is represented by the following Chemical Formula 3, and
  • the positive electrode additive is 0.1 to 7 wt %. At this time, more specifically, the positive electrode additive may be 0.1 to 3.5 wt %.
  • the positive electrode additive is coated with at least one of boron (B) and tungsten (W).
  • the positive electrode additive is decomposed during initial charging and discharging and converted into a Li supply source and a compound represented by Chemical Formula 4 below.
  • the positive electrode additive manufactured according to an exemplary embodiment of the present invention is used for a positive electrode of a lithium secondary battery, and this positive electrode can be usefully used for a lithium secondary battery. That is, the lithium secondary battery according to an exemplary embodiment of the present invention is a positive electrode; negative electrode; and an electrolyte positioned between the positive and negative electrodes, and the positive electrode contains the anode additive mentioned above.
  • a positive electrode active material composition is prepared by mixing a positive electrode additive for a lithium secondary battery, which is a non-reversible capacity improving additive, and a positive electrode active material, conductive material, binder and solvent. After that, it is manufactured by coating and drying directly on an aluminum current collector. Alternatively, the positive active material composition is cast on a separate support. Thereafter, it is possible to manufacture by laminating the film obtained by peeling from the support on an aluminum current collector.
  • the conductive material uses carbon black, graphite, and metal powder
  • the binder is vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacryllonitrile, polymethylmethacrylate, polytetrafluoroethylene and its mixture are possible.
  • a solvent N-methylpyrrolidone, acetone, tetrahydrofuran, decane, etc. are used.
  • the content of the positive active material, conductive material, binder and solvent is used at the level normally used in lithium secondary batteries.
  • the negative active material composition is prepared for the negative electrode by mixing the negative active material, the binder and the solvent like the positive electrode. This can be directly coated on the copper current collector. Alternatively, a negative active material film cast on a separate support and peeled from the support is laminated on a copper current collector. At this time, the negative active material composition may further contain a conductive material if necessary.
  • a material capable of intercalation/deintercalation of lithium for example, lithium metal or lithium alloy, coke, artificial graphite, natural graphite, organic polymer compound combust body, carbon fiber, etc. are used.
  • the conductive material, binder and solvent are used in the same manner as in the case of the anode described above.
  • separators can be used as long as they are commonly used in lithium secondary batteries.
  • polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer of two or more layers thereof may be used.
  • a mixed multilayer such as a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, and a polypropylene/polyethylene/polypropylene three-layer separator can be used.
  • non-aqueous electrolytes or well-known solid electrolytes can be used as electrolytes charged in lithium secondary batteries, and lithium salts dissolved in them are used.
  • the solvent of the non-aqueous electrolyte is not particularly limited, but cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone; ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, and 2-methyltetrahydrofuran; nitriles such as acetonitrile; and amides such as dimethylformamide, etc. can be used. These can be used singly or in a plurality of combinations. Particularly, a mixed solvent of a cyclic carbonate and a chain carbonate can be used. These can
  • an electrolyte a gel polymer electrolyte in which an electrolyte solution is impregnated with a polymer electrolyte such as polyethylene oxide or polyacryllonitrile, or an inorganic solid electrolyte such as LiI or LiN is possible.
  • a polymer electrolyte such as polyethylene oxide or polyacryllonitrile
  • an inorganic solid electrolyte such as LiI or LiN
  • the lithium salt may be one selected from the group consisting of LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiCl, and LiI.
  • NiO and 2.00 molar ratio Li 2 O are weighed according to the molar ratio. After that, they are uniformly mixed and charged into a vacuum furnace (Vacuum furnace). A vacuum was drawn in the vacuum furnace, replaced with nitrogen, and the mixture was calcined while nitrogen was inflowed at 0.1 L/min. The calcining condition was raised to 700° C. for 3 hours and maintained at the elevated temperature for 10 hours. Thereafter, the calcined material was cooled, pulverized and classified into micro powder to obtain a Li 2 NiO 2 positive electrode additive.
  • the mixture was re-calcined while nitrogen was inflowed at 0.1 L/min.
  • the temperature was raised to 380° C. for 2 hours and maintained at the elevated temperature for 5 hours. Thereafter, the calcined material was cooled, pulverized and classified into micro powder to obtain a positive electrode additive.
  • Electrochemical evaluation was performed using a CR2032 coin cell.
  • the prepared slurry was coated on Al foil of 15 ⁇ m thickness using a doctor blade (Doctor blade), then dried and rolled.
  • the electrode loading amount was 14.6 mg/cm 2 , and the rolling density was 3.1 g/cm3.
  • FIG. 1, 2 and Table 1 show the initial charge capacity (0.1C charge) of Li 2 NiO 2 (Comparative Example 1) and Li 6 CoO 4 (exemplary embodiment 1 to 12).
  • Li 2 NiO 2 a comparative example, has a discharge capacity of 120 mAh/g compared to a charge capacity of 380 mAh/g and a non-reversible capacity of about 260 mAh/g.
  • Example 1 shows a non-reversible capacity of about 720 mAh/g with a discharge capacity of 30 mAh/g compared to a 750 mAh/g charge capacity.
  • Example 1 shows a higher non-reversible capacity.
  • Li 2 NiO 2 is changed to LiNiO 2 after charging, causing a gas generation problem as it is continuously decomposed and eluted into NiO during the charging and discharging process.
  • the positive electrode additive which exhibits the effect of improving the non-reversible capacity of Li 6 CoO 4 , decomposes Li 6 CoO 4 after charging and moves six Li to the negative electrode to supplement the non-reversible lithium of the negative electrode.
  • the positive electrode remains LiCoO 2 with good conductivity.
  • O 2 gas generated during charging is removed in the stage of removing generated gas after initial charging and discharging in the completed cell. Since it is stable after that, there is no problem of continuous gas generation during charging and discharging like Li 2 NiO 2 positive electrode additive, so it has greater merit.
  • the samples of Examples 5 to 12 do not have a gelation phenomenon of the cathode material slurry compared to other samples, so there is a merit that there is no problem with the use of a lot of cathode additives that have a non-reversible capacity improvement effect.
  • the boron compound and tungsten compound react with the Li 2 O and Li 2 CO 3 remaining on the surface of the additive to change into stable lithium boron compound (LiB 4 O 7 ) and lithium tungsten compound (Li 2 WO 4 ).
  • it has the merit that it can be used more stably in the electrode manufacturing process by reducing the PVDF binder gelation by basic lithium during slurry manufacturing.
  • the mixing ratio of the doping raw material is preferably 0.001 to 0.02 molar ratio.
  • the positive electrode additive prepared by Example 11 was used for the slurry for the production of electrode plates.
  • Anode additive: anode active material: conductive material (super-C65): binder (PVDF, KF1120) 1:95.5:1.5:2%, and NMP (N-Methyl-2-pyrrolidone) was added so that the solid content was about 30%. was added to adjust the slurry viscosity.
  • the prepared slurry was coated on Al foil of 15 ⁇ m thickness using a doctor blade (Doctor blade), then dried and rolled.
  • the electrode loading amount was 14.6 mg/cm 2 , and the rolling density was 3.1 g/cm3.
  • Comparative Example 2-1 the same experiment was performed using a graphite negative electrode instead of a lithium negative electrode.
  • Table 2 shows the initial charge and discharge capacities (0.2C charge and discharge) of Experimental Examples 2-1 to 2-6, Comparative Example 2-1 and Comparative Example 2-2.
  • a graphite negative electrode is used instead of a lithium negative electrode as in the case of no positive electrode additive (Comparative Examples 2-1 and 2-2), the discharge capacity of 20 mAh/g is reduced due to the non-reversible negative electrode. It compensates for the non-reversible part of the negative electrode as in the case where a lot of positive additive is added (Experimental Examples 2-5, 2-6). Therefore, it shows the same discharge capacity as when using a lithium negative electrode, which has merit to realize stable charging and discharging capacity.
  • the amount of the positive electrode additive can be used by adjusting the optimum amount according to the non-reversible capacity of the negative electrode.
  • the present invention is not limited to the exemplary embodiments and can be manufactured in various different forms, and a person of an ordinary skill in the technical field to which the present invention belongs is without changing the technical idea or essential features of the present invention. It will be understood that the invention may be embodied in other specific forms. Therefore, it should be understood that the exemplary embodiments described above are exemplary in all respects and not restrictive.

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US17/298,778 2018-11-30 2019-11-12 Cathode additive for lithium secondary battery, preparation method therefor, cathode for lithium secondary battery, comprising same, and lithium secondary battery comprising same Pending US20220181627A1 (en)

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KR1020180153090A KR102217302B1 (ko) 2018-11-30 2018-11-30 리튬 이차 전지용 양극 첨가제, 이의 제조방법, 이를 포함하는 리튬 이차 전지용 양극 및 이를 포함하는 리튬 이차 전지
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